Detergent composition containing diimidazoles



Patented July 22 1952 DETERGENT COMPOSITION CONTAINING DIIMIDAZOLES Franz Ackermann, Binningen, and Jules Meyer, 7. 1

Basel, Switzerland, assignors to Ciba Limited, T

a Swiss firm No Drawing. Application March 12, 1948, Serial No. 14,627., In Switzerland March 19, 1947 11 Claims.. *1

According to this invention materials, especially fibrous materials, are improved by treating them at any desired'stage in a process for improving -the materials with a preparation containing an emulsifying agent (including saponaceous detergents) and also at least one asymmetric substitution product of a diimidazole of the general formula Y wherein A is an aromatic radical in which two vicinal carbon atoms are bound to nitrogen atoms of the imidazole rings and R is a bivalent aliphatic radical containing at least One double bond,:all double bonds of the imidazole nuclei and of the radical R forming an uninterrupted series of conjugated double bonds.

The compounds of the above formula do not possess the character of dyestufis, but have a more or less pronounced affinity towards a very wide variety of substrate. Owing to these properties the products of this invention applied to theamaterial by treatment with the indicated compositions of matter, and producing a blue to violet fluorescence in daylight or ultra-violet light, improve the whiteness of undyed materials and the purityof color of dyed materials. In thecase of undyed, originally yellowish materials' the improvement in whiteness becomes apparent by the fact that the applied compound producing a blue to violet fluorescence imparts a white appearance to the originally yellowish material. -If the compositions of matter of the presei'itginytention contain also cleansing agents (of which suitable representatives are indicated be-- low) in addition to the cited diimidazoles, the treatment with such compositions of matter producesfsimultaneously a cleansing efiect. It is thus possible to obtain a brightening effect of high quality on undyed materials especially cel-' lulose materials without impairing the fiber.

Examples of asymmetric substitution products of diimidazoles of the cited general formula wherein A and R have the meanings given above, are those substitution products in which a substituent, for instance an alkyl radical, an alkoxy group or a halogen atom, is contained in only one of the two radicals A. The following compounds may be used: a-[6-chlorobenzimidazyl (2 fl-[benzimidazyl (2) l-ethylene, a-[G- methyl benzimidazyl (2)] 5 [benzimidazyl- (2)1-ethylene, or a [6 methoxy-benzimidazyl-' (2) l-fi- [benzimidazyl- (2) l-ethylene.

Especially advantageous, however, are com-- positions of matter containing at least one-diimidazole of the general formula r or an aralkyl radical, are examples of diimi-- dazoles of the cited formula benzyl-benzimidazyl- (2) -ethylene.

Asymmetrically substituted diimidazoles containing a substituent in only one of the aryl radi cals may be obtained according to th processes described in U. s. Patent No. 2,488,289, issued November 15, 1949. The manufacture of asyni-f metrically substituted diimidazoles containinga substituent on a nitrogen atom 'ofonl'yjone imidazole ring is disclosed and claimed in UtSi i Patent No. 2,515,173, issuedJulyliS, 1950i i.

The processfor improving materials in' accordance with the invention may be carried out impregnating the material tobe-improved with a solution, for "e'x'amplean aqueous solution, or i a dispersion of one of the compositions of matter ,thetic anion-active cleansing agents.

. hereinbefore described, and, after centrifuging or squeezing the material, drying it. Asymmetrically substituted diimidazoles containing an imino group in at least one imidazole ring are soluble in alcohols after conversion into alkali metal salts.

As emulsifying agents the compositionsof matter of this invention maycontain, for ex ample, sulfite cellulose waste liquor or condensation products of naphthalene sulfonic acids which maybe alkylated with formaldehyde; they may also contain saponaceous cleansing agents which, as is known, are also good emulsifying agents. As examples of such saponaceous cleansing agents there are namedordinary soaps/salts of sultuted diimidazoles, in general less than 1 per f jfcent for instance (LOGS-0.5 per cent, are sufficient to increase markedly the efiiciency of defonated washing agents, for example, of sulfonated benzimidazoles substituted at the 2-carbon atom by higher alkyl radicals, further mono carboxylic acid esters of14-sulfophthalic acid having-higher fatty alcohols, and also salts of sulfonated fatty alcohols or condensation products of, higher fatty acids with aliphatic hydroxyor aminosulfonic acids; Such sulfonated washing agents are representatives ,of-thegroup of syn- Y The indicated sulfonated washing agents contain either the sulfonic acid group SO3H or the sulfuric acid ester group -+OSOsI-I, they contain therefore radicals of sulfuric acid. In the compositions of matter ofthis invention. also apolyglycolv periods, thus contrasting favorably with, .the.

known N: Nf -disubstitute d diimidazoles; more:-

over, they may be. better suitable for thetreati-p merit of materialcontaining lime soap, since. they may; cause practically no coloring of :the limesoap stains existing in such material, whereas N:N'-' disubstituted diimidazoles of comparable constitution tend to cause a yellowish coloration of these stains. A particularly pronounced brightening is obtained when unbleached cellulosic material is treated with such mixtures containing washing. agents. 7 H

Thejbmpdsitions of matter used in the process "f.:--of'ithefinvention may alsobe applied in the;-

cgurjse of {the} manufacture Lof the. material to be improved In this case the-compound maybe addeldf'for exampleto a, paper mass or a viscose solution'which isto be used filaments.

The compositions of matter ofgthe invention may also be added, for exampla to liquors used o ma u ms or for imparting a crease resistant finish. They-are also'gsuitable for theafter-treatment of discharge prifits f j}, 4

.I A s' materials which can be improved with the compositions. of matter described above,- there maybe 'xnentioned, for example, the following:

Cellulosic materials, such 5 as cellulose pulp, paper, also textile materials from cotton,linen, regenerated cellulose, including staple fibers of regneratedcellulose; furthermore, natural and ffi fl flgial nitrogenous material, such, as WOOL-silk,

1 ;tergents such as soaps.

In the followingillustrative examples of the mode of preparing the new compounds according to the invention, the parts are parts by weight, unless otherwise stated, and the parts by weight bear the same relation to parts by .volume as do grams to cubic centimeters:

Example 1 I v with onus-0.5 part of a-[benz imidazy [N-hydroxyethyl-benzimidazyl- (2 ,l ethyIene of the formula f \COH=CHO (|3H2CH2OH The mass is allowed to solidify to yield a soaplike preparation. Cellulosicmaterial' which has been. washed with this. preparation. possesses a; whiter appearance than if the material'thad-been washed with thesoap alone. Y

In order to facilitate. its. dispersion .the hindazole derivative may first be dissolved in asmall 7 quantity of alcoholic caustic soda solution or-in.

is poured into waterfand 'the precipitat alcohol alone or in another solve'nt'which ismiscible with water, and-added to the soap in the form of such a solution. Alternatively, the imidazole derivative may first be mixed with a liquid or fused free'fattyacid, and theniconverted into asoap-like preparation in the'usual manner by neutralizing the fatty acid." I

The diimidazole mentioned above may beobtained in the following'man'nerz 24 parts of ethylene chlorhydrin are added in the course of about 2 hours to "a boiling solution of 72 'parts of the acid sulfate of 'a:;9-di-'[ben-" zimidazyl-(2) ]-ethylene in 600 parts of ethyl alcohol andlGO parts of caustic soda solution of: per cent strength; The whole is heatedjat-the' boil for a further 2 hours under reflux', 'and then allowedto 0001. A small quantity of MB-di EN- hydroxyethyl-benzimidazyl-'( 2) T-ethylene whichj precipitates is separated by filtration, the filtrate? a. [benzimidazyl ,(2)lf 18. '[N hydroxyethylf benzimidazyl- (2) l-ethylene is separated by fil1- tration and washed with water. Itcan' be c 5; tained in the pure state by Way of itsfhydrochloride. The new base'so obtained is ia jpale yellow powder which when"dissolvedinalcohol exhibits a violet-blue fluorescence.

Instead of the above diimidazole there may be used a [benzimidazyl-(2)l p-[fi-methyl-benzimidazyl-(2) l-ethylene, or the diimidazole of the formula 5 or an asymmetrically substituted dinaphthimidazole, for example, one with a hydroxy alkyl oup linked to an imidaZole-N-atoms, or a diimidazolej of, the benzene or napthalene series with.;an N-hydroxy-propyl group linked to an,

Example 2 The procedure is the same as that described in Example 1, except that, instead of a- [benzimidazyl (2)] ,8 [N-hydroxyethyl-benzimidazyl- (2)] ethylene, there is used a[benzimidazyl- (2)] B- [N-(dimethylaminoethyl) -benzimidazyl- (2) lethylene of the formula I CH2 By using a- [benzimidazyl- 2) l-fi- [N-idiethylaminoethyl) -benzimidazyl- (2) l-ethylene, which can beobtained from diethyl-fi-chlorethylamine hydrochloride instead of a-[benzimidazyl- (2)] fl [N-(dimethylaminoethyl)-benzimidazyl- (2) l-ethylene,.there is obtaineda soap prep.- aration. having similar properties. l J

The diimidazole mentioned in the first para! graphs may be obtai'nedin the following manner: 'Asolution of 44parts of dimethyl-,B=chlorethyl-.- amine. hydrochloride in 300 parts of ethyl alcohol is added dropwise in the course of 2-3 hours to a boiling solution of 52 parts of aIfl-dl- [benzimidazyl-(Zll-ethylene in 350 parts of ethyl alcohol and 110 parts of ,causticsoda solution of 30,..per cent. strength. The whole is maintained at the boil for about 2 hours longer, filtered-toremove small quantities-of Icy-products, water-is, added to the hot solution until a slight turbidity occurs, and the whole is allowed to cool. 7 I

The condensation product which precipitates is separated by filtration and washed with dilute aqueous alcohol. Itmay be purified by way of its hydrochloride. The resulting 'a-[benzimidazyl-(2) ]-p- [N- (dimethylaminoethyl) benzimidazyl (2) lethylene of the formula I I /N /N O \C CH=OH O \N V IYT/ I (:3H2 H E N(CH3)2 is a bright powder which when dissolved in a1- cohol exhibits a violet -blue fluorescence.

. Example 3 I 0.005- 0.5 part of a-[benzimidazyl-Q)l-fl-[N- methylbenzimidazyl-(Z)l-ethylene is added at '70- 80 C. to a solution of 100 parts of soap in 200 parts of water.

As soonas a homogeneous solution has" been obtained it is allowed to cool. There is obtained I o-orr=onc V a I V a soap-like preparation. Textile goods :which have been washedwith this preparation possess a.

whiterappearance than material which has been washed with soap, alone. The proportion .of the optical bleaching agent used above may be-.de-'

creased or increased.

The diimidazole mentioned above mayq be ob-i tained in the following-manner:

Aqsolution of 104 parts of mB-di-[benzimidazyl-(2)1-ethylene in 500 parts of ethyl alcohol and 221 parts of caustic soda solution of 30 per cent. strength is stirred with 30-40 parts of methyl chloride for about 6 hours in a pressure vessel at-.80 C.

After coolin a small quantity of a:,8- di-[N.,

methylbenzimidazyl-Q)l-ethylene which separatesis removed by filtration, the filtrateis poured into water, and-the precipitate is sep arated by filtration and washed with water. In order to remove residual starting material the product is heated with acetic acid of 25 per cent.

strength, filtered, the filtrate is mixed with am- Easample 4 The procedure is the same as that described in Example 1, except that 0.2 part of a-[benzimid r azyl-(2) p N benzyl benzimidazyl (2) l-' ethylene is used instead of a['benzimida zyl-(2) l-' ,B [N hydroxyethyl benzimidazyl (2) lethylene.

The diimidazole mentioned above may be obtained in the following manner:

32 parts of benzyl chloride are gradually added to a boiling solution of 52 parts of a:,8-di-[ben zimidazyl-(2) ]-ethylene in 320 parts of ethyl alcohol and parts of caustic soda solution of 30 per cent. strength. The whole is stirred for a further 2 hours at the boiling point and then al,- lowed to cool. A small quantity of mfi-di-[N benzyl-benzimidazyl- 2) -ethylene which precipf itates is separated by filtration, the filtrate is poured into water, and the precipitated ll-[benzimidazyl (2)] ,6 [N benzyl-benzimidazyl- 2) l ethylene is separated by filtration, washed withwater'and dried. It is obtained in the pure state by recrystallisation from alcohol. It is a pale yellow powder which exhibits a violet-blue fluorescence in alcoholic solution.

Example 5 There may also be used other arB-di-[benzimidazyl-(2)]-ethy1enes which contain at least one 7 substituent at the nitrogen atoms. There also come into. consideration mixture with other synthetic washing agents, for example, fatty alcohol: sulfonates or condensation products of higher fatty acids with aliphatic hydroxyor The synthetic washing agents'may also be added to mixtures of the foreamino-sulfonic acids.

going benzimidazyl-ethylenes.

As synthetic washing agents there may also be used polyglycollic ethers of higherrfatty'alcohols, furthermore amino carboxylic acids which are acylated' with higher fatty acids. In lieu of the above' 'N-hydroxy-alkyl substitution "products one may use the corresponding N-methylor N-ethyl derivatives. As examples of suitable fatty alcohol sulfonates there may be mentioned those which are derived from lauryl alcohol,

myristic alcohol, cetyl alcohol or olein alcohol.

Example 6' The procedure is the same as that described in Example 1 except that 0.01-0.3 part of a-[benzimidazyl (2)-l fi-[N-ethyl-benzimidazyl-(2)lethylene is used instead of a[benzim dazy1-( 1- 8- [N-hydroxyethyl-benzimidazyl- (2) l -ethylene.

It is also possible to raise the quantity of the diimidazole to, for example, 0.7 per cent.

The diimidazole mentioned above maybe obtained in the following manner:

26 parts of aIB-dl- ['benzimidazyl-(2) l-ethylene are added to a solution of 7 parts of sodium in 660 parts of absolute alcohol. The whole is heated at the boil under reflux, and 17.4 parts of diethyl sulfate are addedto the boiling solution in the course of 2 hours. .The whole is stirred Example 7 The sodiumsalt of sulfonated -heptadecylbenzimidazole is mixed with 0.010.5 per cent of finely pulverizeda-[benzimidazyl-(2)l 3 [N- methy1benzimidazyl-(2) l-ethylene. Undyed tex-. tile goods which have been washed in the usual manner with this mixture possess a higher whiteness than the same material which has been treated onlywith. the aforesaidsodium salt.

. Eatample 8 ..Th e procedure is the same as that described in Example 1 except that Gill-0.3- part. of the diimidazoleof theformula 7 in vhich one :c -represents hydrogen andithe other m 'the. radical. OH:-CH2-CH2-, is usedv instead of a-l'benzimidazyl (2),] -18 [NT -,.hy.droxyethylbenzimidazyl- 2) l -ethylene.

The diimidazole mentioned above may be ob tained in the following manner:

2.7 parts of a- [benzimidazyl- (2) ]-[3- [ti-methylbenzimidazyl-(Z) l-ethylene are added to a boiling solution of 0.7 part ofsodium in 50 parts of alcohol. As soonas dissolution has occurred,

there isadded in thecourse of 1 houra mixture of 1.4 parts'of ethylene chlorhydrin and 5- partsof alcohol.

The whole is maintained ata gentle boil for a further hour, and poured into water; The

precipitated diimidazole of the formula in which one :1: represents hydrogen and the other :1: the residue OH--CH2C'H2- is separated by filtration, washed neutral with water and dried. It may be purified by way of its hydrochloride or by recrystallization from alcohol. It is a pale yellow powder. In alkaline solution it exhibits a violet-blue fluorescence. The abovementioned starting material may be obtained in the following manner:

.19: parts of fi-[benzimidazyl-(Z)l-propionic.

acid; and 12.2 parts of I-methyI-B'AE-diaminobenzene are boiled with parts of hydrochloric. acid of 15 per cent. strength under reflux for 24 The crystals hours, and then allowed. to cool; which precipitate are separated by filtration, if: necessary, the remainder of the diimidazole is separated from. the filtrate: by the addition of? is insoluble in water, by precipitation from a hydrochloric acid solution with ammonia.

5.6 parts of the resulting a-[benzimidazyl- (2 -B- G-methylbenzimidazyl- (2) J -ethane' are dissolved hot in 30 parts of glacial acetic acid, and heated at the gentle boil in a reflux apparatus for 3' hours with a solution of 13.6 parts of' mercuric acetate in 60 parts of glacial acetic acid. After a few minutes there forms in the originally clear reaction solution a thick yellow colored magma which in time becomes thinner. After the heating operation the glacial acetic acid is removed by distillation under reduced pressure. The dry residue is boiled with parts of alcohol and 30 parts of caustic soda solution of 10 per cent strength for a few hours in a reflux apparatus. The reaction mixture is then filtered hot through a folded filter. The clear filtrate is freed from alcohol by distillation. The residue is then acidified with hydrochloric acid, and concentrated ammonia solution is added until the reaction is strongly alkaline. The precipitated dehydrogenation product is separated by filtering with suction, washed neutral with water and dried.

The resulting 11,- [benzimidazyl-(2) l-fi-[G- methyl-benzimidazyl-(2)l-ethylene V isa pale yellow powder which dissolves in alcohol to give solutions which exhibit a strong pale blue. fiuofrescence.

ple. 9 The's odium' salt of the acid sulfuric acid ester of a fatty alcohol mixture as-isobtaii'ied by reducing'co'coanut oil is" mixed witli'0'. 005 to 0.5'per cent of "'finely"pulverized e-[benZimidaZyI-(Z) lfi- I'NL-F hydroxyethyl benzimidazyl (2)]- ethylene. Undyed "textile material which has been washed in the usual manner with theabove mixture presents a whiter appearance than a piece of the same material which has been treated with the above mentioned sodium salt without any addition. I

Example A mixture is made. of 0.05 per cent. finely pulverized afl 6=methy1-benzimidazyl- (2-) ;3- [N- etlf yl-ben zimidazylftz )l-ethylene and soap. Qellulos, material washed {with this preparation presents-a whiter appearance than apiece of the same 'material washed with soap alone."

The above diimidazole can be produced as follows:

77 parts of diethyl sulfate and also caustic soda solution of per cent strength are added in the course of 1 hour at 70-80 C. to-a solution of 38 parts of B-[benzimidazyl-(Z) l-propionic acid in 300 parts of alcohol and parts of caustic sodasolutionof 30 per cent. strength, care ,being taken that the reaction mixture-has an alkaline 'reaction throughout. fmaintained for a;further. hour at the same temhours under reflux, and then allowed to cool.'

The precipitated hydrochloride of w-[N-ethylbenzimidazyl .(2) l.- ,B [6, methyl benzimidazyl-(2)1-ethane is separated by filtration and washed with hydrochloric acid of 1 5 "per cent. strength In*order=to"prepare the base the hydrochloride is dissolved :hot in dilute hydrochloric acid and the base; is precipitated with ammonia, ,The base is separated by filtration,

washed neutral with water',"and1dried.. This a colorless'powder which is" insoluble in water.

6 parts of the resulting a-[N-ethylbenzimid azyl-(2)l fi-[G-methyl-benzimidazyl -(2) l-ethane are dissolved in 30 parts of hot glacial acetic acid, and the solution is heated with a solution of 13.6 parts of mercuric acetate in parts of glacial acetic acid for 1 /2 hours at the gentle boil. After a hort time a yellow magma precipitates which again passes into solution and metallic mercury settles to the bottom. After being heated the solution is poured 01f and the glacial acetic acid is distilled under reduced pressure. The dry residue is digested with bydrochloric acid and then concentrated ammonia solution is added in excess. The precipitated base is separated by filtering with suction, washed neutral with water and then dried. The dry product is extracted at the boil with tetrachlorethane, the solvent is then removed by distillation, and the residue is extracted with alcohol.

By distilling off the alcohol the purified dehydrogenation product is obtained as a residue.

The resulting a.- [N -ethylbenzimidazyl- (2) l-p- [6methylbenzimidazyl(2) l-ethylene is a pale yellow powder which is easily soluble in alcohol. Very dilute alcoholic solutions thereof exhibit a strong violet-blue fluorescence.

Example 11 parts of soap are ground with 20 parts of sodium perborate, 40 parts of sodium metasilicate, and 0.04 part 'of a [benzimidazyl-(21.1%- [N-hydroxyethyl-benzimidazyl- (2) l-ethylene. to formapowder.

Undyed cellulosic material which has been washed in the'ordinary manner in a bath containing the above mixture shows a whiter appearance than such material which has been washed without this diimidazole.

What we claim is:

1. A detergent composition consisting essentially of a water-soluble, synthetic organic,

anion-active. detergent selected from the group consisting of water-soluble soaps and synthetic, organic, non-soap, anion-active, sulfonated detergents containing 0.005 to 1 per cent. by weight of an asymmetric substitution product of a diimidazole of the general formula wherein A is an aromatic radical of-the benzene series in which two vicinal carbon atoms are bound to nitrogen atoms of the imidazole rings and R is an ethylene radical. v

2. A detergent composition consisting" essentially of a water-soluble, synthetic organic, anion-active detergent selected from the group consisting of water-soluble soaps and synthetic organic, non-soap, anion-active, "sulfonated detergents containing 0.005 to l per cent. by weight of diirnidazole of the general formula wherein A is a radical of the benzene series in Whichgtwo vicinal,carbon. atoms are boundto nitrogen? atoms of the imidazole rings and a: is the. nitrogen :atom; of a tertiary amino group connected by its third valence to an aliphatic radical selected from the group consisting of lower alkyl and hydroxyalkyl radicals.

3. A detergent composition consisting of a water-soluble soap containing 0.005 to 0.5 per cent by weight of a diimidazole of the general formula wherein A is a radical of the benzene series in which two vicinal carbon atoms are bound to nitrogen atoms of the imidazole rings and a: is the nitrogen atom of a tertiary amino group, connected by its third valence to an aliphatic radical selected from the group consisting of lower alkyl and hydroxyalkyl radicals.

4. A detergent composition consisting of a 11 water-soluble soap containing 0.005 .to 0.5 per cent by weight of a diimidazole of the general formula I MW r wherein R is a lower alkyl radical.

5. A detergent composition consisting of a water-soluble soap containing 0.005 to 0.5 .per cent by weight of the diimidazole of the formula Ill CEzCHa. v

6.7 A detergent composition consisting of a water-soluble soap containing 0.005 to 0.5 percent by weight of a diimidazole of the'general formula wherein R is a hydroxyalkyl radical.

'7. A detergent composition consisting of a water-soluble soap containing 0.005 to 0.5 per cent by weightof the rdiimidazolelof theformula 8'. :A detergent composition consisting of a Watepsoluble, synthetic organic, non-soap, anionactive, sulfonated detergent containing 0.005 to 0.5 per cent by weight'of a diimidazole of the general formula wherein A is a radical of the benzene series in whichrtwo vicinal carbon atoms are bound to nitrogen atoms of the imidazole rings and :c'is

J12 the, nitrogen atom of a tertiary amino group, connected with its third valence to an aliphatic radical selected from the .group-;consisting of alkyl and-hydroxyalkylradicals; ,9. A detergent composition consistingrofwa water-soluble, synthetic organic non-seamenionactive, sulfuric acid ester'detergent containing 0.005 to 0.5 per centby weightof a diim-idazole of the general formula.

F I 10 H whereinR is aihydroxyalkyl radical. 1 10. A detergentlcompos'ition consisting of a water-soluble salt of a sulfuric acid. ester-of a no fatty alcohol containingiatlleastll) carbonatoms and 0.005 'to 0.5 vper cent by weight .ofuthewdie imidazole of the formula 0 j on-roman 11. A detergent composition consis tingpf a water-soluble saltof a sulfuric'acid ester "of a mixture of fatty alcohoiscontaining 1'0"to"1'6 carbon atoms and-0.005 to 10.5;per' cent by weight of the diirnidazol'e'of theformula i omcmon V FRANZ ACKERDMNN.

REFERENCES CITED; 4

The following references are of record inthe file of "this patent:

UNITED STATES PATENTS I Number 7 Name I Date a 1 2,463,264 Graenacher'et a1; Mar. 1. 194 V FOREIGN PATENTS Number Country Date 731,558 Germany. lFeb. 11,-:1943 55 584,484; 

1. A DETERGENT COMPOSITION CONSISTING ESSENTIALLY OF A WATER-SOLUBLE, SYNTHETIC ORGANIC, ANION-ACTIVE DETERGENT SELECTED FROM THE GROUP CONSISTING OF WATER-SOLUBLE SOAPS AND SYNTHETIC, ORGANIC, NON-SOAP, ANION-ACTIVE, SULFONATED DETERGENTS CONTAINING 0.005 TO 1 PER CENT. BY WEIGHT OF AN ASYMMETRIC SUBSTITUTION PRODUCT OF A DIIMIDAZOLE OF THE GENERAL FORMULA 